Ethyl 3-mercaptobutyrate as a flavoring or fragrance agent and methods for preparing and using same

ABSTRACT

This invention pertains to a method for flavoring an ingestible composition with a flavoring agent in organoleptically purified form, unaccompanied by substances of natural origin present in mango. The flavoring agent may be used in a wide variety of ingestible vehicles such as chewing gum compositions, hard and soft confections, dairy products, beverage products including juice drinks and juice products, green vegetable and chicken products, and the like. The present invention also pertains to an ingestible composition comprising an ingestible vehicle and an organoleptically effective amount of the purified flavoring agent. The present invention further pertains to ethyl 3-mercaptobutyrate represented by the formula, CH 3 (SH)CHCH 2 COOCH 2 CH 3 , in purified form, unaccompanied by substances of natural origin present in mango. The present invention still further pertains to a method to confer, enhance, improve, or modify the odor properties of a perfuming composition or a perfumed article, which comprises adding to the perfuming composition or perfumed article, ethyl 3-mercaptobutyrate represented by the formula, CH 3 (SH)CHCH 2 COOCH 2 CH 3 . The present invention still further pertains to a perfuming composition or a perfumed article containing as an active perfuming ingredient, ethyl 3-mercaptobutyrate represented by the formula, CH 3 (SH)CHCH 2 COOCH 2 CH 3 . The present invention also pertains to a method for preparing ethyl 3-mercaptobutyrate which comprises reacting ethyl crotonate with sodium hydrogen sulfide and sodium bicarbonate to form the disulfide dimer of ethyl 3-mercaptobutyrate followed by reducing the disulfide dimer to yield ethyl 3-mercaptobutyrate.

This is a continuation application of patent application Ser. No.10/007,095, filed Dec. 4, 2001 now abandoned.

This application claims priority from United Kingdom patent applicationserial no. 0009769.1, filed Apr. 19, 2000.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention pertains to a method for flavoring an ingestiblecomposition with a flavoring agent in organoleptically purified form,unaccompanied by substances of natural origin present in mango. Theflavoring agent may be used in a wide variety of ingestible vehiclessuch as chewing gum compositions, hard and soft confections, dairyproducts, beverage products including juice drinks and juice products,green vegetable and chicken products, and the like. The presentinvention also pertains to an ingestible composition comprising aningestible vehicle and an organoleptically effective amount of thepurified flavoring agent. The present invention further pertains toethyl 3-mercaptobutyrate represented by the formula,CH₃(SH)CHCH₂COOCH₂CH₃, in purified form, unaccompanied by substances ofnatural origin present in mango. The present invention still furtherpertains to a method to confer, enhance, improve, or modify the odorproperties of a perfuming composition or a perfumed article, whichcomprises adding to the perfuming composition or perfumed article, ethyl3-mercaptobutyrate represented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃.The present invention still further pertains to a perfuming compositionor a perfumed article containing as an active perfuming ingredient,ethyl 3-mercaptobutyrate represented by the formula,CH₃(SH)CHCH₂COOCH₂CH₃. The present invention also pertains to a methodfor preparing ethyl 3-mercaptobutyrate which comprises reacting ethylcrotonate with sodium hydrogen sulfide and sodium bicarbonate to formthe disulfide dimer of ethyl 3-mercaptobutyrate followed by reducing thedisulfide dimer to yield ethyl 3-mercaptobutyrate.

2. Description of the Background

The Generessence™ flavor research program conducted by Bush Boake Allenfocuses on developing flavors by employing in depth understanding of thevolatile organic components present in a wide variety of samples, forexample fruits and herbs and coupling this information to flavorpreference profiling. A number of sampling and analytical techniques areused including extraction and headspace analyses often including thesampling of growing fruit or flowers. The flavors are primarilyformulated from synthetic chemicals and contain only componentsidentified in the sample. There is no limit to the concentration ofindividual components used apart from organoleptic considerations. Aproblem with developing flavoring agents for fruity and herbaceousmaterials, such as mango flavor, is that natural plant materials do notcontain a single flavoring agent, but rather contain a complex mixtureof volatile components making identification of characteristic flavorsvery difficult. The volatiles of mango were analyzed by gaschromatography and a combined gas chromatograph-mass spectrometer. Thevolatiles were also analyzed by gas chromatography on a sulfur detector.

U.S. Pat. No. 4,180,672 (Kurozumi et al.) disclosesorganodithiocyclopentanes said to inhibit ulcer formation. Theorganodithiocyclopentanes have at position 1, a carbonyl group, ahydroxyl group, or a protected hydroxyl group; at position 2, —S—R,wherein R is a monovalent organic group containing 1 to 25 carbon atoms;at position 3, —S—R′, —CH₂—R′—, or —CH═R′, wherein R′ is a monovalent ordivalent organic group containing 1 to 25 carbon atoms; and at position4, a hydrogen atom, a hydroxyl group, or a protected hydroxyl group.When positions 1 and 4 are both a hydroxyl group or a protected hydroxylgroup, position 3 is —S—R′. Kurozumi et al. also discloses2-organothio-2-cyclopentenones wherein position 2 and position 4 are asdefined above.

U.S. Pat. No. 4,189,505 (Mosher) discloses a flavorant for imparting apork-like flavor to foodstuffs. The flavorant is obtained by reacting atan elevated temperature in an edible liquid reaction medium a mixture of(a) a source of an amino acid, (b) a lower aliphatic mercaptocarboxylicacid, and (c) oleoresin sage. The mixture contains from about 5 to about300 parts by weight of amino acid source per part by weight ofmercaptocarboxylic acid and from about 0.005 to about 0.3 part by weightof oleoresin sage per part by weight of mercaptocarboxylic acid.

U.S. Pat. No. 4,229,588 (Louthan'588) discloses a method for preparingdialkyl dithiodialkanoates said to be useful as paint preservatives. Themethod comprises contacting a halogen with a mercaptoalkyl ester of theformula, R′—O—C—R—SH. R is an alkylene radical having from 1 to 12carbon atoms and R′ is an alkyl radical having from 1 to 12 carbonatoms. The mole ratio of halogen to mercaptoalkyl ester is between 04:1to 0.6:1. The reaction produces a first liquid phase of dialkyldithiodialkanoate having the formula, R′—O—CO—R—S—S—R—CO—O—R′, and aseparate, second liquid phase of hydrocarbon solvent. Representativemercaptoalkyl ester reagents are methylmercaptoacetate, methyl3-mercaptopropionate, methyl 2-mercaptopropionate, methyl4-mercaptobutyrate, methyl 3-mercaptobutyrate, methyl2-mercaptobutyrate, methyl 5-mercaptovalerate, methyl6-mercaptocaproate, ethyl 2-mercaptoacetate, ethyl 3-mercaptopropionate,propyl 3-mercaptopropionate, isopropyl 3-mercaptopropionate, andcyclohexyl 3-mercaptopropionate.

U.S. Pat. No. 4,232,167 (Louthan'167) discloses a method of preparingmixed esters said to be useful as paint preservatives. The methodcomprises reacting hydrogen sulfide with an olefinically unsaturatedcarboxylate of the formula, CR₂═CR₄(CR₂)_(n)CO₂R′, wherein R′ is analkyl radical containing 1 to 5 carbon atoms and R is hydrogen or R′.The integer n is zero or an integer having the value of 1, 2, or 3. Thetotal number of carbon atoms in all of the R and R′ groups is 1 to 15per molecule. Alkyl mercaptocarboxylates which are produced arerepresented by the formula, HS—(CR₂)_(p)CO₂R′, wherein R and R′ are asdescribed above and p is an integer having a value of from 2 to 5.Examples of alkyl mercaptocarboxylates include methyl2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl4-mercaptobutyrate, n-butyl 6-mercaptohexanoate, isopropyl6-mercaptoundecanoate, n-pentyl6-mecapto-2-(2,2-dimethylpropyl)undecanoate, t-butyl2-mercapto-2-methylheptanoate, methyl 3,3-dimethyl-6-mercaptohexanoate,and n-propyl 6-mercapto-2,2,3,3,4,4,5,5,6-nonamethylheptanoate.

U.S. Pat. No. 4,433,134 (Louthan'134) discloses a method for preparingalkyl mercaptoalkanoates said to be useful as paint preservatives. Themethod comprises reacting carbon dioxide containing hydrogen sulfidewith an olefinically unsaturated carboxylate of the formulaCR₂═CR(CR₂)_(p)CO₂R′. R′ is an alkyl radical containing from 1 to 5carbon atoms; each R is selected independently from hydrogen and R′; pis selected from 0, 1, 2, and 3; and the total number of carbon atoms inall the R groups does not exceed 15. Examples of alkylmercaptoalkanoates produced by the catalyzed addition reaction and usedin the transesterification reaction include methyl mercaptoacetate,methyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl4-mercaptobutyrate, n-butyl6-mercaptohexanoate, isopropyl6-mercaptoundecancate, n-pentyl6-mercapto-2-(3-methyl-1-butyl)undecancate, t-butyl2-mercapto-2-methylheptaneate, methyl 3,3-dimethyl-6-mercaptohexanoate,and n-propyl 6-mercapto-2,2,3,3,4,4,5,5,6-nonamethylheptanoate.

U.S. Pat. No. 5,008,432 (Roberts) discloses a process for producingmercapto-substituted compounds. The process comprises passing a mixtureof hydrogen sulfide and an olefinically unsaturated compound in whichthe double bond is conjugated with an activating group selected from thegroup consisting of carbonyl, carboxyl, carboxylate, carboxamide,nitrile, nitro, and sulfoxide. The alkyl mercaptoalkanoates which can beproduced by the catalyzed addition reaction and used in thetransesterification reaction include ethyl 4-mercaptobutyrate.

While the above disclosure provides some insight into flavoringcomponents, the above disclosure does not provide satisfactory flavoringagents. The present invention provides a novel flavoring agent withoutthe disadvantages which are characteristic of previously known products.The present invention also provides methods for preparing and using theflavoring agents and the ingestible compositions in which it may beemployed.

SUMMARY OF THE INVENTION

The present invention is directed at a method for flavoring aningestible composition which comprises admixing an ingestible vehiclewith an organoleptically effective amount of ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,unaccompanied by substances of natural origin present in mango.

The present invention is also directed at an ingestible compositioncomprising (i) an ingestible vehicle; and (ii) an organolepticallyeffective amount of ethyl 3-mercaptobutyrate represented by the formula,CH₃(SH)CHCH₂COOCH₂CH₃, in purified form, unaccompanied by substances ofnatural origin present in mango.

The present invention is further directed at ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,unaccompanied by substances of natural origin present in mango.

The present invention is further directed at a method to confer,enhance, improve, or modify the odor properties of a perfumingcomposition or a perfumed article, which comprises adding to theperfuming composition or perfumed article, ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃. The present inventionis further directed at a perfuming composition or a perfumed articlecontaining as an active perfuming ingredient, ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃.

The present invention is further directed at a method for preparingethyl 3-mercaptobutyrate which comprises reacting ethyl crotonate withsodium hydrogen sulfide and sodium bicarbonate to form the disulfidedimer of ethyl 3-mercaptobutyrate followed by reducing the disulfidedimer of ethyl 3-mercaptobutyrate to yield ethyl 3-mercaptobutyrate.

DETAILED DESCRIPTION OF THE INVENTION

Applicant has discovered that ethyl 3-mercaptobutyrate,CH₃(SH)CHCH₂COOCH₂CH₃, possesses unexpected flavor properties andimparts a unique note to flavors, especially for conferring infoodstuffs in which it is incorporated a green, mango, fruity odor and agreen, sulfur, sweet, muscat grape, fruity, blackcurrant, tropical andfleshy flavor. A relatively large number of components were identifiedin an analysis of mango. The compounds were tentatively identified byinterpretation of their mass spectra and gas chromatographic data andconfirmed by synthesis and analysis (IR, NMR and mass spectra). Amongthe components identified in the solvent extract of mango was ethyl3-mercaptobutyrate. Ethyl 3-mercaptobutyrate was synthesized for use asan analytical standard for confirmation of the identification. Thecompound was believed to be of good flavor interest since the materialhad been targeted with the aid of gas chromatographic odor experiments.Ethyl 3-mercaptobutyrate was found to possess unique flavorcharacteristics and has been successfully incorporated into commerciallyviable flavors. Ethyl 3-mercaptobutyrate was also found to possessunique fragrance characteristics and has been successfully incorporatedinto commercially viable fragrances. Although the absolute concentrationof this ester in mango was not determined, the ester is present at suchlow concentrations in mango that it cannot be isolated from the fruit ina commercially viable way.

The following terms are used throughout the specification and aredefined as follows unless otherwise indicated.

The terms “ingestible” and “edible”, as used herein, refer to allmaterials and compositions which are used by or which perform a functionin the body. These materials and compositions include those which areadsorbed and those which are not absorbed as well as those which aredigestible and non-digestible.

The terms “flavor”, “flavoring”, and “flavorant”, as used herein, areused interchangeably whenever an organoleptic compound is referred towhich is intended to stimulate the sense of taste and smell.

The term “organoleptic”, as used herein, refers to compounds of theinvention which stimulate the sense of smell or taste, and are thusperceived as having a characteristic odor and/or flavor. The term“organoleptically acceptable solvent”, as used herein, refers tosolvents which do not stimulate the sense of smell or taste, and arethus perceived as not having a characteristic odor and/or flavor. Theterm “organoleptically effective amount”, as used herein, means a levelor amount of flavoring compound(s) present in a material at which theincorporated compound(s) exhibit(s) a sensory effect.

In accord with the present invention, applicant has discovered a methodfor flavoring an ingestible composition. The method comprises admixingan ingestible vehicle with an organoleptically effective amount of ethyl3-mercaptobutyrate represented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, inpurified form, unaccompanied by substances of natural origin present inmango.

As set out above, ethyl 3-mercaptobutyrate was synthesized for use as ananalytical standard for confirmation of the identification. Ethyl3-mercaptobutyrate was prepared by reacting ethyl crotonate with sodiumhydrogen sulfide and sodium bicarbonate in water, at room temperature,to form the disulfide dimer of the product.

Disulfide Dimer of Ethyl 3-Mercaptobutyrate

The disulfide dimer of ethyl 3-mercaptobutyrate was then reduced withzinc in acetic acid to yield the desired product, ethyl3-mercaptobutyrate.

Distillation of the crude material at 76–80° C. and 10 mmHg gave ethyl3-mercaptobutyrate in 50% yield and 97% purity.

Ethyl 3-mercaptobutyrate is of use in the formulation of flavoringcompositions, especially for conferring in foodstuffs in which it isincorporated a green, mango, fruity sulphurous odor and a green, sulfur,sweet, muscat grape, fruity, blackcurrant, tropical and fleshy flavor,when used at a dose level of 0.1–10 ppb.

The flavoring agent of the present invention may be used in manydistinct physical forms well known in the flavoring art to provide aninitial dosage of the flavoring agent and/or a further time-release formof the flavoring agent. Without being limited thereto, such physicalforms include free forms and encapsulated forms, and mixtures thereof.

The flavoring agent may be used in a wide variety of ingestiblevehicles. Nonlimiting examples of suitable ingestible vehicles includechewing gum compositions, hard and soft confections, dairy products,beverage products including juice products and soft drinks, and thelike. The combination of the flavoring agent of the present inventiontogether with an ingestible vehicle and optional ingredients, whendesired, provides a flavoring agent that possesses unexpected flavorvalue and imparts a unique note to a wide variety of flavors, especiallytropical flavors such as mango flavor.

In a preferred embodiment, the invention is directed at an ingestiblecomposition comprising (i) an ingestible vehicle; and (ii) anorganoleptically effective amount of ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,unaccompanied by substances of natural origin present in mango.Preferably, the ingestible composition is a beverage product, aconfectionery composition, or a chewing gum.

The flavoring agent may further comprise an organoleptically acceptablesolvent. The organoleptically acceptable solvent may be any solventwhich does not interfere with the organoleptic properties of theflavoring agents of the present invention. In general, theorganoleptically acceptable solvent does not stimulate the sense ofsmell or taste, and is not perceived as having a characteristic odorand/or flavor. Illustrative nonlimiting examples of organolepticallyacceptable solvents may be selected from the group consisting ofpropylene glycol, ethanol, triacetin, glycerol, and vegetable oils. Whenemployed, the organoleptically acceptable solvent will be present in anamount from about 1% to about 99%, preferably from about 5% to about90%, and more preferably from about 20% to about 80%, by weight.

The amount of the inventive flavoring agent employed in an ingestiblecomposition is an organoleptically effective amount to provide aflavoring agent that exhibits a sensory effect. The exact amount offlavoring agent used may vary depending upon the type of flavoring agentemployed, the type of ingestible vehicle employed, and the level offlavor desired. In general, the amount of flavoring agent present is theordinary dosage required to obtain the desired result. Such dosages areknown to the skilled practitioner in the confectionery arts and are nota part of the present invention. In a preferred embodiment, theflavoring agent in the flavoring agent is present in an amount fromabout 0.001% to about 1%, preferably from about 0.01% to about 0.75%,and more preferably from about 0.1% to about 0.50%, by weight.

In the method for flavoring an ingestible composition of the presentinvention, the ingestible composition is prepared by admixing theflavoring agent in an ingestible vehicle, together with any optionalingredients, to form a uniform mixture. The final compositions arereadily prepared using standard methods and apparatus generally known bythose skilled in the confectionery arts. The apparatus useful inaccordance with the present invention comprises mixing apparatus wellknown in the confectionery arts, and therefore the selection of thespecific apparatus will be apparent to the artisan.

In another embodiment, the present invention is directed at ethyl3-mercaptobutyrate represented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, inpurified form, unaccompanied by substances of natural origin present inmango.

In yet another embodiment, the present invention is directed at a methodto confer, enhance, improve, or modify the odor properties of aperfuming composition or a perfumed article, which comprises adding tothe perfuming composition or perfumed article, ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃. Preferably, ethyl3-mercaptobutyrate is present in the perfuming composition or perfumedarticle in an amount from about 0.001% to about 1%, by weight, morepreferably ethyl 3-mercaptobutyrate is present in the perfumingcomposition or perfumed article in an amount from about 0.1% to about0.50%, by weight.

In still yet another embodiment, the present invention is directed at aperfuming composition or a perfumed article containing as an activeperfuming ingredient, ethyl 3-mercaptobutyrate represented by theformula, CH₃(SH)CHCH₂COOCH₂CH₃. Preferably, the perfumed article is inthe form of a perfume or a cologne, a soap, a bath or shower gel, ashampoo or other hair care product, a body deodorant, an air freshener,a detergent or fabric softener, or a household cleaner.

When used for perfuming functional articles, like soaps, bath or showergels shampoos or other hair care products, cosmetic preparations, bodydeodorants or air fresheners, detergents or fabric softeners, orhousehold products, lower concentrations are generally employed. Thevalues of these concentrations depend on the nature of the article orfinal perfumed product as well as on the desired olfactory effect, and aperson skilled in the art will be capable of choosing these as afunction of these parameters. Articles, such as perfuming or deodorizingproducts may thus typically contain from about 0.1% to about 1% byweight of a perfuming composition prepared according to the presentinvention.

In still yet another embodiment, the present invention is directed at amethod for preparing ethyl 3-mercaptobutyrate which comprises reactingethyl crotonate with sodium hydrogen sulfide and sodium bicarbonate toform the disulfide dimer of ethyl 3-mercaptobutyrate followed byreducing the disulfide dimer of ethyl 3-mercaptobutyrate to yield ethyl3-mercaptobutyrate.

An important aspect of the present invention includes an improvedchewing gum composition incorporating the inventive flavoring agent anda method for preparing the chewing gum composition, including bothchewing gum and bubble gum formulations. In general, the improvedchewing gum compositions will contain a gum base, a bulking agent, anorganoleptically effective amount of a flavoring agent, and variousadditives such as a flavoring agent.

The chewing gum compositions may be reduced-calorie chewing gumsemploying high levels of a chewing gum base having an enhancedhydrophilic character. These reduced-calorie chewing gums will comprisea gum base present in an amount from about 50% to about 85%, preferablyfrom about 50% to about 75%, and more preferably from about 60% to about70%, by weight of the chewing gum composition. When a reduced-calorieproduct is not desired, the chewing gum composition may contain loweramounts of a chewing gum base. These chewing gums will comprise a gumbase present in an amount up to about 55%, preferably from about 15% toabout 40%, and more preferably from about 20% to about 35%, by weight ofthe chewing gum composition.

As used herein, the term “reduced-calorie composition” means acomposition having a caloric value two thirds or less than that of aconventional composition. The term “tight” or “rubbery” chew refers to achewing gum composition which requires a large amount of muscularchewing effort to masticate or to a composition which provides a gumbolus with high elasticity and bounce and which is difficult to deform.

Gum bases having an enhanced hydrophilic character include polyvinylacetate gum bases which may also contain a low melting point wax. Suchgum bases do not require a high level of bulking agent to plasticize thegum base and render it soft during chewing. These gum bases may be usedat higher than normal levels in chewing gum compositions in place of abulking and/or a bulk sweetening agent to prepare high base-low bulkingagent reduced-calorie gums which do not have rubbery or tight chewcharacteristics. These gum bases possess increased hydrophilicproperties over conventional gum bases and appear to increase in sizeduring chewing releasing flavoring and sweetening agents which wouldnormally be entrapped in the gum base while maintaining a soft chewtexture. Reduced-calorie chewing gum compositions prepared with such gumbases in high levels are less hygroscopic (have lower moisture-pickup)and are less prone to becoming stale than conventional reduced-caloriegum compositions while having comparable firmness and texture.

The elastomers (rubbers) employed in the gum base of the presentinvention will vary greatly depending upon various factors such as thetype of gum base desired, the consistency of gum composition desired andthe other components used in the composition to make the final chewinggum product. The elastomer may be any water-insoluble polymer known inthe art, and includes those gum polymers utilized for chewing gums andbubble gums. Illustrative examples of suitable polymers in gum basesinclude both natural and synthetic elastomers. For example, thosepolymers which are suitable in gum base compositions include, withoutlimitation, natural substances (of vegetable origin) such as chicle,natural rubber, crown gum, nispero, rosidinha, jelutong, perillo, nigergutta, tunu, balata, guttapercha, lechi capsi, sorva, gutta kay, and thelike, and mixtures thereof. Examples of synthetic elastomers include,without limitation, styrene-butadiene copolymers (SBR), polyisobutylene,isobutylene-isoprene copolymers, polyethylene, and the like, andmixtures thereof.

The amount of elastomer employed in the gum base will vary greatlydepending upon various factors such as the type of gum base used, theconsistency of the gum composition desired and the other components usedin the composition to make the final chewing gum product. In general,the elastomer will be present in the gum base in an amount from about0.5% to about 20%, and preferably from about 2.5% to about 15%, byweight of the gum base.

The polyvinyl acetate polymer employed in the gum base of the presentinvention is a polyvinyl acetate polymer having a medium molecularweight, specifically, having a mean average molecular weight in therange from about 35,000 to about 55,000. This medium molecular weightpolyvinyl acetate polymer will preferably have a viscosity from about 35seconds to about 55 seconds (ASTM designation D1200-82 using a Ford cupviscometer procedure). The medium molecular weight polyvinyl acetatepolymer will be present in the gum base in an amount from about 10% toabout 25%, and preferably from about 12% to about 27%, by weight of thegum base.

The medium molecular weight polyvinyl acetate polymer may also beblended with a low molecular weight polyvinyl acetate polymer. The lowmolecular weight polyvinyl acetate polymer will have a mean averagemolecular weight in the range from about 12,000 to about 16,000. Thislow molecular weight polyvinyl acetate polymer will preferably have aviscosity from about 14 seconds to about 16 seconds (ASTM designationD1200-82 using a Ford cup viscometer procedure). The low molecularweight polyvinyl acetate polymer will be present in the gum base in anamount up about 17%, and preferably from about 12% to about 17%, byweight of the gum base.

When a low molecular weight polyvinyl acetate polymer is blended with amedium molecular weight polyvinyl acetate polymer, the polymers will bepresent in a mole ratio from about 1:0.5 to about 1:1.5, respectively.

The medium molecular weight polyvinyl acetate polymer may also beblended with a high molecular weight polyvinyl acetate polymer. The highmolecular weight polyvinyl acetate polymer will have a mean averagemolecular weight in the range from about 65,000 to about 95,000. Thehigh molecular weight polyvinyl acetate polymer will be present in thegum base in an amount up to about 5%, by weight of the gum base.

The acetylated monoglycerides in the present invention, like thepolyvinyl acetate polymer, serve as plasticizing agents. While thesaponification value of the acetylated monoglycerides is not critical,preferable saponification values are 278 to 292, 316 to 331, 370 to 380,and 430 to 470. A particularly preferred acetylated monoglyceride has asaponification value above about 400. Such acetylated monoglyceridesgenerally have an acetylation value (percentage acetylated) above about90 and a hydroxyl value below about 10 (Food Chemical Codex (FCC)III/P508 and the revision of AOCS).

The use of acetylated monoglycerides in the present gum base ispreferred over the use of bitter polyvinyl acetate (PVA) plasticizers,in particular, triacetin. The acetylated monoglycerides will be presentin the gum base in an amount from about 4.5% to about 10%, andpreferably from about 5% to about 9%, by weight of the gum base.

The wax in the gum base of the present invention softens the polymericelastomer mixture and improves the elasticity of the gum base. The waxesemployed will have a melting point below about 60° C., and preferablybetween about 45° C. and about 55° C. A preferred wax is low meltingparaffin wax. The wax will be present in the gum base in an amount fromabout 6% to about 10%, and preferably from about 7% to about 9.5%, byweight of the gum base.

In addition to the low melting point waxes, waxes having a highermelting point may be used in the gum base in amounts up to about 5%, byweight of the gum base. Such high melting waxes include beeswax,vegetable wax, candelilla wax, carnauba wax, most petroleum waxes, andthe like, and mixtures thereof.

In addition to the components set out above, the gum base includes avariety of traditional ingredients, such as a component selected fromthe group consisting of elastomer solvents, emulsifiers, plasticizers,fillers, and mixtures thereof. These ingredients are present in the gumbase in an amount to bring the total amount of gum base to 100%.

The gum base may contain elastomer solvents to aid in softening theelastomer component. Such elastomer solvents may comprise thoseelastomer solvents known in the art, for example, terpinene resins suchas polymers of alpha-pinene or beta-pinene, methyl, glycerol andpentaerythritol esters of rosins and modified rosins and gums, such ashydrogenated, dimerized and polymerized rosins, and mixtures thereof.Examples of elastomer solvents suitable for use herein include thepentaerythritol ester of partially hydrogenated wood and gum rosin, thepentaerythritol ester of wood and gum rosin, the glycerol ester of woodrosin, the glycerol ester of partially dimerized wood and gum rosin, theglycerol ester of polymerized wood and gum rosin, the glycerol ester oftall oil rosin, the glycerol ester of wood and gum rosin and thepartially hydrogenated wood and gum rosin and the partially hydrogenatedmethyl ester of wood and rosin, and the like, and mixtures thereof. Theelastomer solvent may be employed in the gum base in amounts from about2% to about 15%, and preferably from about 7% to about 11%, by weight ofthe gum base.

The gum base may also include emulsifiers which aid in dispersing theimmiscible components into a single stable system. The emulsifiersuseful in this invention include glyceryl monostearate, lecithin, fattyacid monoglycerides, diglycerides, propylene glycol monostearate, andthe like, and mixtures thereof. A preferred emulsifier is glycerylmonostearate. The emulsifier may be employed in amounts from about 2% toabout 15%, and preferably from about 7% to about 11%, by weight of thegum base.

The gum base may also include plasticizers or softeners to provide avariety of desirable textures and consistency properties. Because of thelow molecular weight of these ingredients, the plasticizers andsofteners are able to penetrate the fundamental structure of the gumbase making it plastic and less viscous. Useful plasticizers andsofteners include lanolin, palmitic acid, oleic acid, stearic acid,sodium stearate, potassium stearate, glyceryl triacetate, glyceryllecithin, glyceryl monostearate, propylene glycol monostearate,acetylated monoglyceride, glycerine, and the like, and mixtures thereof.Waxes, for example, natural and synthetic waxes, hydrogenated vegetableoils, petroleum waxes such as polyurethane waxes, polyethylene waxes,paraffin waxes, microcrystalline waxes, fatty waxes, sorbitanmonostearate, tallow, propylene glycol, mixtures thereof, and the like,may also be incorporated into the gum base. The plasticizers andsofteners are generally employed in the gum base in amounts up to about20%, and preferably in amounts from about 9% to about 17%, by weight ofthe gum base.

Preferred plasticizers are the hydrogenated vegetable oils and includesoybean oil and cottonseed oil which may be employed alone or incombination. These plasticizers provide the gum base with good textureand soft chew characteristics. These plasticizers and softeners aregenerally employed in amounts from about 5% to about 14%, and preferablyin amounts from about 5% to about 13.5%, by weight of the gum base.

In another preferred embodiment, the softening agent is anhydrousglycerin, such as the commercially available United States Pharmacopeia(USP) grade. Glycerin is a syrupy liquid with a sweet warm taste and hasa sweetness of about 60% of that of cane sugar. Because glycerin ishygroscopic, it is important that the anhydrous glycerin be maintainedunder anhydrous conditions throughout the preparation of the chewing gumcomposition.

The gum base of this invention may also include effective amounts ofbulking agents such as mineral adjuvants which may serve as fillers andtextural agents. Useful mineral adjuvants include calcium carbonate,magnesium carbonate, alumina, aluminum hydroxide, aluminum silicate,talc, tricalcium phosphate, dicalcium phosphate, and the like, andmixtures thereof. These fillers or adjuvants may be used in the gum basecompositions in various amounts. Preferably the amount of filler, whenused, will be present in an amount from about 15% to about 40%, andpreferably from about 20% to about 30%, by weight of the gum base.

A variety of traditional ingredients may be optionally included in thegum base in effective amounts such as coloring agents, antioxidants,preservatives, flavoring agents, and the like. For example, titaniumdioxide and other dyes suitable for food, drug and cosmeticapplications, known as F. D. & C. dyes, may be utilized. An anti-oxidantsuch as butylated hydroxyanisole (BHA), propyl gallate, and mixturesthereof, may also be included. Other conventional chewing gum additivesknown to one having ordinary skill in the chewing gum art may also beused in the gum base.

The manner in which the gum base components are admixed is not criticaland is performed using standard techniques and apparatus known to thoseskilled in the art. In a typical method, an elastomer is admixed with anelastomer solvent and/or a plasticizer and/or an emulsifier and agitatedfor a period of from 1 to 30 minutes. After blending is complete, thepolyvinyl acetate component is admixed into the mixture. The mediummolecular weight polyvinyl acetate is preferably admixed prior toaddition of the optional low molecular weight polyvinyl acetate toprevent the creation of pockets of polyvinyl acetate within theelastomer mixture. The remaining ingredients, such as the low meltingpoint wax, are then admixed, either in bulk or incrementally, while thegum base mixture is blended again for 1 to 30 minutes.

In one embodiment, the invention pertains to a reduced-calorie chewinggum composition which comprises a gum base present in an amount fromabout 40% to about 75%, by weight of the chewing gum composition, whichcomprises (a) an elastomer present in an amount from about 0.5% to about20%, by weight of the gum base, (b) a medium molecular weight polyvinylacetate polymer having a molecular weight from about 35,000 to about55,000 present in an amount from about 10% to about 25%, by weight ofthe gum base, (c) an acetylated monoglyceride present in an amount fromabout 4.5% to about 10%, by weight of the gum base, (d) a wax having amelting point below about 60° C. present in an amount from about 6% toabout 10%, by weight of the gum base, and (e) a material selected fromthe group consisting of elastomer solvents, emulsifiers, plasticizers,fillers, and mixtures thereof, present in an amount to bring the totalamount of gum base to 100%, by weight of the gum base.

Chewing gum compositions employing a high level of a chewing gum basehaving an enhanced hydrophilic character are more fully described inU.S. Pat. No. 4,872,884, which disclosure is incorporated herein byreference.

Other gum bases having an enhanced hydrophilic nature and suitable foruse in reduced-calorie chewing gum compositions in high levels may alsobe employed in the present invention. In general, these gum bases may beemployed in amounts up to 99%, preferably from about 40% to about 85%,and more preferably from about 40% to about 75%, by weight of thechewing gum composition. Suitable gum bases having an enhancedhydrophilic nature include, for example, those disclosed in U.S. Pat.No. 4,698,223, which disclosure is incorporated herein by reference. Thegum base is formulated with the inventive flavoring agent andconventional additives such as a bulking agent to prepare a wide varietyof sweetened chewing gum compositions.

The amount of gum base employed in the chewing gum composition will varydepending on such factors as the type of gum base used, the consistencydesired, and the other components used to make the final chewing gumproduct. In general, the gum base having an enhanced hydrophiliccharacter will be present in the chewing gum composition in an amountfrom about 50% to about 85%, preferably from about 50% to about 75%, andmore preferably from about 60% to about 70%, by weight of the chewinggum composition.

In another embodiment, the invention pertains to a chewing gumcomposition which contains lower amounts of a chewing gum base. Ingeneral, the gum base in these chewing gum compositions will be presentin an amount up to about 55%, preferably from about 15% to about 40%,and more preferably from about 20% to about 35%, by weight of thechewing gum composition. In this embodiment, the gum base will comprisean elastomer and a variety of traditional ingredients such as anelastomer solvent, waxes, emulsifiers, plasticizers or softeners,bulking agents such as mineral adjuvants which may serve as fillers andtextural agents, coloring agents, antioxidants, preservatives, flavoringagents, and the like, and mixtures thereof. Illustrative examples ofthese gum base components have been set out above.

Once prepared, the gum base may be formulated with the flavoring agentof the present invention and conventional additives to prepare a widevariety of chewing gum compositions.

The chewing gum compositions generally include bulking agents. Thesebulking agents (carriers, extenders) may be water-soluble and includebulking agents selected from the group consisting of, but not limitedto, monosaccharides, disaccharides, polysaccharides, sugar alcohols, andmixtures thereof; isomalt (a mixture ofalpha-D-glucopyranosyl-1,6-mannitol andalpha-D-glucopyranosyl-1,6-sorbitol manufactured under the tradenamePalatinit by Suddeutsche Zucker), maltodextrins; hydrogenated starchhydrolysates; hydrogenated hexoses; hydrogenated disaccharides;minerals, such as calcium carbonate, talc, titanium dioxide, dicalciumphosphate, celluloses and the like, and mixtures thereof. Bulking agentsmay be used in amounts up to about 60%, and preferably in amounts fromabout 25% to about 60%, by weight of the chewing gum composition.

Suitable sugar bulking agents include monosaccharides, disaccharides andpolysaccharides such as xylose, ribulose, glucose (dextrose), mannose,galactose, fructose (levulose), sucrose (sugar), maltose, invert sugar,partially hydrolyzed starch and corn syrup solids, and mixtures thereof.When the chewing gum composition is a sugar gum, mixtures of sucrose andcorn syrup solids are the preferred sugar bulking agents.

Suitable sugar alcohol bulking agents include sorbitol, xylitol,mannitol, galactitol, maltitol, and mixtures thereof. Mixtures ofsorbitol and mannitol are the preferred sugar alcohol bulking agents.

Maltitol is a sweet, non-caloric, water-soluble sugar alcohol useful asa bulking agent in the preparation of non-caloric beverages andfoodstuffs and is more fully described in U.S. Pat. No. 3,708,396, whichdisclosure is incorporated herein by reference. Maltitol is made byhydrogenation of maltose which is the most common reducing disaccharideand is found in starch and other natural products.

The chewing gum compositions may also include a high intensitysweetening agent (sweeteners). High intensity sweetening agents have asweetness intensity substantially greater than that of sucrose. Suitablehigh intensity sweetening agents include water-soluble naturalsweetening agents such as dihydrochalcones, monellin, Stevia Rebaudiana(steviosides), glycyrrhizin, and mixtures thereof. Suitablewater-soluble artificial sweetening agents include saccharin and itssoluble salts, i.e., sodium and calcium saccharin salts, cyclamate andits salts, 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(Acesulfame) and the sodium, ammonium, and calcium salts thereof, andespecially the potassium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide (Acesulfame-K).

Suitable dipeptide based sweetening agents include L-aspartic acidderived sweetening agents such as L-aspartyl-L-phenylalanine methylester (Aspartame), compounds described in U.S. Pat. No. 3,492,131,L-alpha-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl) -D-alaninamihydrate (Alitame), methyl esters of L-aspartyl-L-phenylglycerine andL-aspartyl-L-2,5-dihydrophenylglycine,L-aspartyl-2,5-dihydro-L-phenyl-alanine, andL-aspartyl-L-(1-cyclohexen)alanine.

Other suitable water-soluble sweetening agents include those derivedfrom naturally occurring water-soluble sweetening agents such aschlorinated derivatives of sucrose, e.g., chlorodeoxysugar derivativessuch as derivatives of chlorodeoxysucrose andchlorodeoxy-galactosucrose. Examples of chlorodeoxysucrose andchlorodeoxygalactosucrose derivatives include but are not limited to1-chloro-1′-deoxysucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-alpha-D-fructofuranoside, or4-chloro-4-deoxygalactosucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-1-chloro-1-deoxy-beta-D-fructo-furanoside,or 4,1′-dichloro-4,1′-dideoxygalactosucrose;1′,6′-dichloro-1′,6′-dideoxysucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructo-furanoside,or 4,1′,6′-trichloro-4,1′,6′-trideoxygalacto-sucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-6-chloro-6-deoxy-beta-D-fructo-furanoside,or 4,6,6′-trichloro-4,6,6′-trideoxygalacto-sucrose;6,1′,6′-trichloro-6,1′,6′-trideoxysucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-di-deoxy-beta-D-fructofuranoside,or 4,6,1′,6′-tetrachloro-4,6,1′,6′-tetradeoxygalacto-sucrose; and4,6,1′,6′-tetrachloro-4,6,1′,6′-tetradeoxy-sucrose. In a preferredembodiment, the chlorodeoxysugar derivative is4,1′,6′-trichloro-4,1′,6′-trideoxygalacto-sucrose, or4-chloro-4-deoxy-alpha-D-galactopyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructofuranoside,which is commercially available under the tradename Sucralose fromMcNeil Specialty Products Company, Skillman, N.J.

Other suitable high intensity sweetening agents include protein basedsweetening agents such as talin (thaumaoccous danielli, Thaumatin I andII).

The amount of the high intensity sweetening agent employed in thechewing gum composition is an effective amount to sweeten the chewinggum. In general, the amount of high intensity sweetening agent normallypresent in a chewing gum composition will be from about 0.001% to about1%, preferably from about 0.01% to about 1%, and more preferably fromabout 0.05% to about 0.5%, by weight of the chewing gum composition.

The gum composition may include effective amounts of conventionaladditives selected from the group consisting of plasticizers, softeners,emulsifiers, waxes, fillers, mineral adjuvants, flavoring agents(flavors, flavorings), coloring agents (colorants, colorings),antioxidants, acidulants, thickening agents, and the like, and mixturesthereof. These ingredients are present in the chewing gum composition inan amount to bring the total amount of chewing gum composition to 100%.Some of these additives may serve more than one purpose. For example, insugarless gum compositions, a sweetening agent, such as sorbitol orother sugar alcohol, may also function as a bulking agent.

The plasticizers, softening agents, mineral adjuvants, waxes andantioxidants discussed above, as being suitable for use in the gum base,may also be used in the chewing gum composition. Examples of otherconventional additives which may be used include emulsifiers, such aslecithin and glyceryl monostearate, thickening agents, used alone or incombination with other softeners, such as methyl cellulose, alginates,carrageenan, xanthan gum, gelatin, carob, tragacanth, and locust bean,acidulants such as malic acid, adipic acid, citric acid, tartaric acid,fumaric acid, and mixtures thereof, and fillers, such as those discussedabove under the category of mineral adjuvants.

The flavoring agents which may be used include those flavors known tothe skilled artisan, such as natural and artificial flavors. Theseflavorings may be chosen from synthetic flavor oils and flavoringaromatics and/or oils, oleoresins and extracts derived from plants,leaves, flowers, fruits, and so forth, and combinations thereof.Nonlimiting representative flavor oils include vanilla, spearmint oil,cinnamon oil, oil of wintergreen (methyl salicylate), peppermint oil,clove oil, bay oil, anise oil, eucalyptus oil, thyme oil, cedar leafoil, oil of nutmeg, allspice, oil of sage, mace, oil of bitter almonds,and cassia oil. Also useful flavorings are natural and synthetic fruitflavors such as citrus oils including lemon, orange, lime, grapefruit,and fruit essences including apple, pear, peach, grape, strawberry,raspberry, cherry, plum, pineapple, apricot and so forth. Theseflavoring agents may be used in liquid or solid form and may be usedindividually or in admixture. Commonly used flavors include mints suchas peppermint, menthol, artificial vanilla, cinnamon derivatives, andvarious fruit flavors, whether employed individually or in admixture.

Other useful flavorings include aldehydes and esters such as cinnamylacetate, cinnamaldehyde, citral diethylacetal, dihydrocarvyl acetate,eugenyl formate, p-methylamisol, and so forth may be used. Generally anyflavoring or food additive such as those described in Chemicals Used inFood Processing, publication 1274, pages 63–258, by the National Academyof Sciences, may be used.

Further examples of aldehyde flavorings include but are not limited toacetaldehyde (apple), benzaldehyde (cherry, almond), anisic aldehyde(licorice, anise), cinnamic aldehyde (cinnamon), citral, i.e.,alpha-citral (lemon, lime), neral, i.e., beta-citral (lemon, lime),decanal (citrus fruits such as orange, lemon), ethyl vanillin (vanilla,cream), heliotrope, i.e., piperonal (vanilla, cream), vanillin (vanilla,cream), alpha-amyl cinnamaldehyde (spicy fruity flavors), butyraldehyde(butter, cheese), valeraldehyde (butter, cheese), citronellal (modifies,many types), aldehyde C-8 (citrus fruits), aldehyde C-9 (citrus fruits),aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde (berry fruits),hexenal, i.e., trans-2 (berry fruits), tolyl aldehyde (cherry, almond),veratraldehyde (vanilla), 2,6-dimethyl-5-heptenal, i.e., melonal(melon), 2,6-dimethyloctanal (green fruit), and 2-dodecenal (citrus,mandarin), cherry, grape, strawberry shortcake, mixtures thereof and thelike.

The flavoring agent may be employed in either liquid form and/or driedform. When employed in the latter form, suitable drying means such asspray drying the oil may be used. Alternatively, the flavoring agent maybe absorbed onto water soluble materials, such as cellulose, starch,sugar, maltodextrin, gum arabic and so forth or may be encapsulated. Theactual techniques for preparing such dried forms are well known and donot constitute a part of this invention.

The flavoring agents of the present invention may be used in manydistinct physical forms well known in the art to provide an initialburst of flavor and/or a prolonged sensation of flavor. Without beinglimited thereto, such physical forms include free forms, such as spraydried, powdered, and beaded forms, and encapsulated forms, and mixturesthereof.

Encapsulated delivery systems for flavoring agents or sweetening agentscomprise a hydrophobic matrix of fat or wax surrounding a sweeteningagent or flavoring agent core. The fats may be selected from any numberof conventional materials such as fatty acids, glycerides orpolyglycerol esters, sorbitol esters, and mixtures thereof. Examples offatty acids include hydrogenated and partially hydrogenated vegetableoils such as palm oil, palm kernel oil, peanut oil, rapeseed oil, ricebran oil, soybean oil, cottonseed oil, sunflower oil, safflower oil, andmixtures thereof. Glycerides which are useful include monoglycerides,diglycerides, and triglycerides.

Waxes useful may be chosen from the group consisting of natural andsynthetic waxes, and mixtures thereof. Non-limiting examples includeparaffin wax, petrolatum, carbowax, microcrystalline wax, beeswax,carnauba wax, candellila wax, lanolin, bayberry wax, sugarcane wax,spermaceti wax, rice bran wax, and mixtures thereof.

The fats and waxes may be use individually or in combination in amountsvarying from about 10 to about 70%, and preferably in amounts from about40 to about 58%, by weight of the encapsulated system. When used incombination, the fat and wax are preferably present in a ratio fromabout 70:10 to 85:15, respectively.

Typical encapsulated flavoring agent or sweetening agent deliverysystems are disclosed in U.S. Pat. Nos. 4,597,970 and 4,722,845, whichdisclosures are incorporated herein by reference.

The amount of flavoring agent employed herein is normally a matter ofpreference subject to such factors as the type of final chewing gumcomposition, the individual flavor, the gum base employed, and thestrength of flavor desired. Thus, the amount of flavoring may be variedin order to obtain the result desired in the final product and suchvariations are within the capabilities of those skilled in the artwithout the need for undue experimentation. In gum compositions, theflavoring agent is generally present in amounts from about 0.02% toabout 5%, and preferably from about 0.1% to about 2%, and morepreferably, from about 0.8% to about 1.8%, by weight of the chewing gumcomposition.

The coloring agents useful in the present invention are used in amountseffective to produce the desired color. These coloring agents includepigments which may be incorporated in amounts up to about 6%, by weightof the gum composition. A preferred pigment, titanium dioxide, may beincorporated in amounts up to about 2%, and preferably less than about1%, by weight of the gum composition. The colorants may also includenatural food colors and dyes suitable for food, drug and cosmeticapplications. These colorants are known as F.D.& C. dyes and lakes. Thematerials acceptable for the foregoing uses are preferablywater-soluble. Illustrative nonlimiting examples include the indigoiddye known as F.D.& C. Blue No.2, which is the disodium salt of5,5′-indigotindisulfonic acid. Similarly, the dye known as F.D.& C.Green No.1 comprises a triphenylmethane dye and is the disodium salt of4-[4-(N-ethyl-p-sulfoniumbenzylamino)diphenylmethylene]-[1-(N-ethyl-N-p-sulfoniumbenzyl)-delta-2,5-cyclohexadienimine].A full recitation of all F.D.& C. colorants and their correspondingchemical structures may be found in the Kirk-Othmer Encyclopedia ofChemical Technology, 3rd Edition, in volume 5 at pages 857–884, whichtext is incorporated herein by reference.

Suitable oils and fats usable in gum compositions include partiallyhydrogenated vegetable or animal fats, such as coconut oil, palm kerneloil, beef tallow, lard, and the like. These ingredients when used aregenerally present in amounts up to about 7%, and preferably up to about3.5%, by weight of the gum composition.

In accordance with this invention, organoleptically effective amounts ofthe flavoring agent of the present invention may be admixed into thechewing gum composition. The exact amount of flavoring agent employed isnormally a matter of preference subject to such factors as theparticular type of gum composition being prepared, the type of bulkingagent employed, the type of flavor employed, and the intensity of breathfreshening perception desired. Thus, the amount of flavoring agent maybe varied in order to obtain the result desired in the final product andsuch variations are within the capabilities of those skilled in the artwithout the need for undue experimentation. In general, the amount offlavoring agent normally present in a chewing gum composition will befrom about 0.001% to about 20%, preferably from about 0.01% to about15%, more preferably from about 0.1% to about 10%, and most preferablyfrom about 0.1% to about 5%, by weight of the chewing gum composition.

In a preferred embodiment, the present invention is directed to achewing gum composition comprising:

-   (i) a gum base;-   (ii) a bulking agent; and-   (iii) an organoleptically effective amount of ethyl    3-mercaptobutyrate, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,    unaccompanied by substances of natural origin present in mango.

The present invention also includes a method for preparing the improvedchewing gum compositions, including both chewing gum and bubble gumformulations. The chewing gum compositions may be prepared usingstandard techniques and equipment known to those skilled in the art. Theapparatus useful in accordance with the present invention comprisesmixing and heating apparatus well known in the chewing gum manufacturingarts, and therefore the selection of the specific apparatus will beapparent to the artisan.

In such a method, a chewing gum composition is made by admixing the gumbase with the flavoring agent and the other ingredients of the finaldesired chewing gum composition. Other ingredients will usually beincorporated into the composition as dictated by the nature of thedesired composition as well known by those having ordinary skill in theart. The ultimate chewing gum compositions are readily prepared usingmethods generally known in the food technology and chewing gum arts.

For example, the gum base is heated to a temperature sufficiently highto soften the base without adversely effecting the physical and chemicalmake up of the base. The optimal temperatures utilized may varydepending upon the composition of the gum base used, but suchtemperatures are readily determined by those skilled in the art withoutundue experimentation.

The gum base is conventionally melted at temperatures that range fromabout 60° C. to about 120° C. for a period of time sufficient to renderthe base molten. For example, the gum base may be heated under theseconditions for a period of about thirty minutes just prior to beingadmixed incrementally with the remaining ingredients of the gumcomposition such as the inventive flavoring agent, plasticizer, thesoftener, the bulking agent, and/or fillers, coloring agents andflavoring agents to plasticize the blend as well as to modulate thehardness, viscoelasticity and formability of the base. Mixing iscontinued until a uniform mixture of gum composition is obtained.Thereafter the gum composition mixture may be formed into desirablechewing gum shapes.

In a preferred embodiment, the invention is directed at a method forpreparing a chewing gum composition which comprises the steps of:

-   (1) providing the following ingredients:    -   (i) a gum base;    -   (ii) a bulking agent; and    -   (iii) an organoleptically effective amount of a flavoring agent;-   (2) melting the gum base;-   (3) admixing the bulking agent and the flavoring agent with the    melted gum base; and-   (4) forming the mixture from step (C) into suitable shapes.

The flavoring agent is prepared according to the method of the presentinvention.

Another important aspect of the present invention includes aconfectionery composition incorporating the inventive flavoring agentand a method for preparing the confectionery compositions. Thepreparation of confectionery formulations is historically well known andhas changed little through the years. Confectionery items have beenclassified as either “hard” confectionery or “soft” confectionery. Theflavoring agents of the present invention can be incorporated into theconfections by admixing the inventive composition into the conventionalhard and soft confections.

Hard confectionery may be processed and formulated by conventionalmeans. In general, a hard confectionery has a base composed of a mixtureof sugar and other carbohydrate bulking agents kept in an amorphous orglassy condition. The hard confectionery may also be sugarless. Thisform is considered a solid syrup of sugars generally having from about0.5% to about 1.5% moisture. Such materials normally contain up to about92% sugar, up to about 55% corn syrup and from about 0.1% to about 5%water, by weight of the final composition. The syrup component isgenerally prepared from sucrose and corn syrups, but may include othermaterials. Further ingredients such as flavorings, sweetening agents,acidulants, colorants and so forth may also be added.

Such confectionery may be routinely prepared by conventional methodssuch as those involving fire cookers, vacuum cookers, andscraped-surface cookers also referred to as high speed atmosphericcookers.

Fire cookers involve the traditional method of making a candy base. Inthis method, the desired quantity of carbohydrate bulking agent isdissolved in water by heating the agent in a kettle until the bulkingagent dissolves. Additional bulking agent may then be added and cookingcontinued until a final temperature of 145° C. to 156° C. is achieved.The batch is then cooled and worked as a plastic-like mass toincorporate additives such as flavoring agent, colorants and the like.

A high-speed atmospheric cooker uses a heat-exchanger surface whichinvolves spreading a film of candy on a heat exchange surface, the candyis heated to 165° C. to 170° C. in a few seconds. The candy is thenrapidly cooled to 100° C. to 120° C. and worked as a plastic-like massenabling incorporation of the additives, such as flavoring agent,colorants and the like.

In vacuum cookers, the carbohydrate bulking agent is boiled to 125° C.to 132° C., vacuum is applied and additional water is boiled off withoutextra heating. When cooking is complete, the mass is a semi-solid andhas a plastic-like consistency. At this point, flavoring agent,colorants, and other additives are admixed in the mass by routinemechanical mixing operations.

The optimum mixing required to uniformly mix the flavoring agent,colorants and other additives during conventional manufacturing of hardconfectionery is determined by the time needed to obtain a uniformdistribution of the materials. Normally, mixing times of from 2 to 10minutes have been found to be acceptable.

Once the candy mass has been properly tempered, it may be cut intoworkable portions or formed into desired shapes. A variety of formingtechniques may be utilized depending upon the shape and size of thefinal product desired. A general discussion of the composition andpreparation of hard confections may be found in H. A. Lieberman,Pharmaceutical Dosage Forms: Tablets, Volume 1 (1989), Marcel Dekker,Inc., New York, N.Y. at pages 419 to 582, which disclosure isincorporated herein by reference.

The apparatus useful in accordance with the present invention comprisescooking and mixing apparatus well known in the confectionerymanufacturing arts, and therefore the selection of the specificapparatus will be apparent to the artisan.

In contrast, compressed tablet confections contain particular materialsand are formed into structures under pressure. These confectionsgenerally contain sugars in amounts up to about 95%, by weight of thecomposition, and typical tablet excipients such as binders andlubricants as well as flavoring agent, colorants and so forth. Theseconfections may also be sugarless.

Similar to hard confectionery, soft confectionery may be utilized inthis invention. The preparation of soft confections, such as nougat,involves conventional methods, such as the combination of two primarycomponents, namely (1) a high boiling syrup such as a corn syrup, or thelike, and (2) a relatively light textured frappe, generally preparedfrom egg albumin, gum arabic, gelatin, vegetable proteins, such as soyderived compounds, sugarless milk derived compounds such as milkproteins, and mixtures thereof. The frappe is generally relativelylight, and may, for example, range in density from about 0.5 to about0.7 grams/cc.

The high boiling syrup, or “bob syrup” of the soft confectionery isrelatively viscous and has a higher density than the frappe component,and frequently contains a substantial amount of carbohydrate bulkingagent. Conventionally, the final nougat composition is prepared by theaddition of the “bob syrup” to the frappe under agitation, to form thebasic nougat mixture. Further ingredients such as flavoring, additionalcarbohydrate bulking agent, colorants, preservatives, medicaments,mixtures thereof and the like may be added thereafter also underagitation. Soft confectioneries may also be prepared sugarless. Ageneral discussion of the composition and preparation of nougatconfections may be found in B. W. Minifie, Chocolate, Cocoa andConfectionery: Science and Technology, 2nd edition, AVI Publishing Co.,Inc., Westport, Conn. (1983), at pages 576–580, which disclosure isincorporated herein by reference.

The procedure for preparing the soft confectionery involves knownprocedures. In general, the frappe component is prepared first andthereafter the syrup component is slowly added under agitation at atemperature of at least about 65° C., and preferably at least about 100°C. The mixture of components is continued to be mixed to form a uniformmixture, after which the mixture is cooled to a temperature below 80°C., at which point, the flavor may be added. The mixture is furthermixed for an additional period until it is ready to be removed andformed into suitable confectionery shapes.

In accordance with this invention, organoleptically effective amounts ofthe flavoring agents of the present invention may be admixed into thehard and soft confections. The exact amount of flavoring agent employedis normally a matter of preference subject to such factors as theparticular type of confection being prepared, the type of bulking agentor carrier employed, the type of flavor employed and the intensity ofbreath freshening perception desired. Thus, the amount of flavoringagent may be varied in order to obtain the result desired in the finalproduct and such variations are within the capabilities of those skilledin the art without the need for undue experimentation. In general, theamount of flavoring agent normally present in a hard or soft confectionwill be from about 0.001% to about 20%, preferably from about 0.01% toabout 15%, more preferably from about 0.1% to about 10%, and mostpreferably from about 0.1% to about 5%, by weight of the confection.

In a preferred embodiment, the present invention is directed to aconfectionery composition comprising:

-   (i) a confectionery bulking agent; and-   (ii) an organoleptically effective amount of ethyl    3-mercaptobutyrate, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,    unaccompanied by substances of natural origin present in mango.

The present invention extends to methods for making the improvedconfections. The flavoring agents may be incorporated into an otherwiseconventional hard or soft confection composition using standardtechniques and equipment known to those skilled in the art. Theapparatus useful in accordance with the present invention comprisesmixing and heating apparatus well known in the confectionerymanufacturing arts, and therefore the selection of the specificapparatus will be apparent to the artisan.

In such a method, a composition is made by admixing the inventiveflavoring agent into the confectionery composition along with the otheringredients of the final desired composition. Other ingredients willusually be incorporated into the composition as dictated by the natureof the desired composition as well known by those having ordinary skillin the art. The ultimate confectionery compositions are readily preparedusing methods generally known in the food technology and pharmaceuticalarts. Thereafter the confectionery mixture may be formed into desirableconfectionery shapes.

The flavoring agents may be formulated with conventional ingredientswhich offer a variety of textures to suit particular applications. Suchingredients may be in the form of hard and soft confections, tablets,toffee, nougat, chewy candy, chewing gum and so forth, center filledcandies, both sugar and sugarless. The acceptable ingredients may beselected from a wide range of materials. Without being limited thereto,such materials include diluents, binders and adhesives, lubricants,disintegrants, bulking agents, humectants and buffers and adsorbents.The preparation of such confections and chewing gum products is wellknown.

The flavoring agents may also be in the form of a pharmaceuticalsuspension. Pharmaceutical suspensions of this invention may be preparedby conventional methods long established in the art of pharmaceuticalcompounding. Suspensions may contain adjunct materials employed informulating the suspensions of the art. The suspensions of the presentinvention can comprise:

(a) preservatives such as butylated hydroxyanisole (BHA), benzoic acid,ascorbic acid, methyl paraben, propyl paraben, tocopherols, and thelike, and mixtures thereof. Preservatives are generally present inamounts up to about 1%, and preferably from about 0.05% to about 0.5%,by weight of the suspension;

(b) buffers such as citric acid-sodium citrate, phosphoric acid-sodiumphosphate, and acetic acid-sodium acetate in amounts up to about 1%, andpreferably from about 0.05% to about 0.5%, by weight of the suspension;

(c) suspending agents or thickeners such as cellulosics likemethylcellulose, carrageenans like alginic acid and its derivatives,xanthan gums, gelatin, acacis, and microcrystalline cellulose in amountsup to about 20%, and preferably from about 1% to about 15%, by weight ofthe suspension;

(d) antifoaming agents such as dimethyl polysiloxane in amounts up toabout 0.2%, and preferably from about 0.01% to about 0.1%, by weight ofthe suspension;

(e) sweetening agents such as those sweeteners well known in the art,including both natural and artificial sweeteners. Sweetening agents suchas monosaccharides, disaccharides and polysaccharides such as xylose,ribose, glucose (dextrose), mannose, galactose, fructose (levulose),sucrose (sugar), maltose, invert sugar (a mixture of fructose andglucose derived from sucrose), partially hydrolyzed starch, corn syrupsolids, dihydrochalcones, monellin, steviosides, glycyrrhizin, and sugaralcohols such as sorbitol, mannitol, maltitol, hydrogenated starchhydrolysates and mixtures thereof may be utilized in amounts up to about60%, and preferably from about 20% to about 50%, by weight of thesuspension. Water-soluble artificial sweeteners such as solublesaccharin salts, i.e., sodium or calcium saccharin salts, cyclamatesalts, the sodium, ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(Acesulfame-K), the free acid form of saccharin, and the like may beutilized in amounts from about 0.001% to about 5%, by weight of thesuspension;

(f) flavoring agents such as those flavors well known to the skilledartisan, such as natural and artificial flavors and mints, such aspeppermint, menthol, citrus flavors such as orange and lemon, artificialvanilla, cinnamon, various fruit flavors, both individual and mixed andthe like may be utilized in amounts from about 0.01% to about 5%, byweight of the suspension;

(g) coloring agents such as pigments which may be incorporated inamounts up to about 6%, by weight of the suspension. A preferredpigment, titanium dioxide, may be incorporated in amounts up to about2%, and preferably less than about 1%, by weight of the suspension. Thecoloring agents may also include natural food colors and dyes suitablefor food, drug and cosmetic applications. These colorants are known asF.D.& C. dyes and lakes. The materials acceptable for the foregoing usesare preferably water-soluble. Such dyes are generally present in amountsup to about 0.25%, and preferably from about 0.05% to about 0.2%, byweight of the suspension;

(h) decolorizing agents such as sodium metabisulfite, ascorbic acid andthe like may be incorporated into the suspension to prevent colorchanges due to aging. In general, decolorizing agents may be used inamounts up to about 0.25%, and preferably from about 0.05% to about0.2%, by weight of the suspension; and

(i) solubilizers such as alcohol, propylene glycol, polyethylene glycol,and the like may be used to solubilize the flavoring agents. In general,solubilizing agents may be used in amounts up to about 10%, andpreferably from about 2% to about 5%, by weight of the suspension.

The pharmaceutical suspensions of the present invention may be preparedas follows:

(A) admix the thickener with water heated from about 40° C. to about 95°C., preferably from about 40° C. to about 70° C., to form a dispersionif the thickener is not water soluble or a solution if the thickener iswater soluble;

(B) admix the sweetening agent with water to form a solution;

(C) admix the flavoring agent with the thickener-water admixture to forma uniform thickener-flavoring agent;

(D) combine the sweetener solution with the thickener-flavoring agentand mix until uniform; and

(E) admix the optional adjunct materials such as coloring agents,flavoring agents, decolorants, solubilizers, antifoaming agents, buffersand additional water with the mixture of step (D) to form thesuspension.

The flavoring agents of this invention may also be in chewable form. Toachieve acceptable stability and quality as well as good taste and mouthfeel in a chewable formulation several considerations are important.These considerations include the amount of active substance per tablet,the flavoring agent employed, the degree of compressibility of thetablet and the organoleptic properties of the composition.

Chewable candy is prepared by procedures similar to those used to makesoft confectionery. In a typical procedure, a boiled sugar-corn syrupblend is formed to which is added a frappe mixture. The boiledsugar-corn syrup blend may be prepared from sugar and corn syrup blendedin parts by weight ratio of about 90:10 to about 10:90. The sugar-cornsyrup blend is heated to temperatures above about 120° C. to removewater and to form a molten mass. The frappe is generally prepared fromgelatin, egg albumin, milk proteins such as casein, and vegetableproteins such as soy protein, and the like, which is added to a gelatinsolution and rapidly mixed at ambient temperature to form an aeratedsponge like mass. The frappe is then added to the molten candy mass andmixed until homogeneous at temperatures between about 65° C. and about120° C.

The composition of the instant invention can then be added to thehomogeneous mixture as the temperature is lowered to about 65° C.–95° C.whereupon additional ingredients can then be added such as flavoringagents and coloring agents. The formulation is further cooled and formedinto pieces of desired dimensions.

A general discussion of the lozenge and chewable tablet forms ofconfectionery may be found in H. A. Lieberman and L. Lachman,Pharmaceutical Dosage Forms: Tablets Volume 1, Marcel Dekker, Inc., NewYork, N.Y. (1989) at pages 367 to 418, which disclosure is incorporatedherein by reference.

In accordance with this invention, organoleptically effective amounts ofthe flavoring agents of the present invention may be admixed into thehard and soft confectionery products. These amounts are readilydetermined by those skilled in the art without the need for undueexperimentation. In a preferred embodiment, the flavoring agent willcomprise the flavoring agent in an amount from about 0.25% to about 2%and an ingestible vehicle, that is a pharmaceutically acceptablecarrier, in a quantity sufficient to bring the total amount ofcomposition to 100%, by weight the ingestible composition. In a morepreferred embodiment, the composition will comprise the flavoring agentin an amount from about 0.05% to about 1% and an ingestible vehicle in aquantity sufficient to bring the total amount of composition to 100%, byweight the ingestible composition.

In another form of the invention, the flavoring agent is incorporatedinto an ingestible topical vehicle which may be in the form of amouthwash, rinse, ingestible spray, suspension, dental gel, and thelike. Typical non-toxic ingestible vehicles known in the pharmaceuticalarts may be used in the present invention. The preferred ingestiblevehicles are water, ethanol, and water-ethanol mixtures. Thewater-ethanol mixtures are generally employed in a weight ratio fromabout 1:1 to about 20:1, preferably from about 3:1 to about 20:1, andmost preferably from about 3:1 to about 10:1, respectively. The pH valueof the ingestible vehicle is generally from about 4 to about 7, andpreferably from about 5 to about 6.5. An ingestible topical vehiclehaving a pH value below about 4 is generally irritating to theingestible cavity and an ingestible vehicle having a pH value greaterthan about 7 generally results in an unpleasant mouth feel.

The ingestible topical flavoring agents may also contain conventionaladditives normally employed in those products. Conventional additivesinclude a fluorine providing compound, a sweetening agent, a flavoringagent, a coloring agent, a humectant, a buffer, and an emulsifier,providing the additives do not interfere with the flavoring propertiesof the composition.

The coloring agents and humectants, and the amounts of these additivesto be employed, set out above,may be used in the ingestible topicalcomposition.

Fluorine providing compounds may be fully or slightly water soluble andare characterized by their ability to release fluoride ions or fluoridecontaining ions in water and by their lack of reaction with othercomponents in the composition. Typical fluorine providing compounds areinorganic fluoride salts such as water-soluble alkali metal, alkalineearth metal, and heavy metal salts, for example, sodium fluoride,potassium fluoride, ammonium fluoride, cuprous fluoride, zinc fluoride,stannic fluoride, stannous fluoride, barium fluoride, sodiumfluorosilicate, ammonium fluorosilicate, sodium fluorozirconate, sodiummonofluorophosphate, aluminum mono- and di-fluorophosphates andfluorinated sodium calcium pyrophosphate. Alkali metal fluorides, tinfluoride and monofluorophosphates, such as sodium and stannous fluoride,sodium monofluorophosphate and mixtures thereof, are preferred.

The amount of fluorine providing compound present in the presentingestible topical composition is dependent upon the type of fluorineproviding compound employed, the solubility of the fluorine compound,and the nature of the final ingestible composition. The amount offluorine providing compound used must be a nontoxic amount. In general,the fluorine providing compound when used will be present in an amountup to about 1%, preferably from about 0.001% to about 0.1%, and mostpreferably from about 0.001% to about 0.05%, by weight of the ingestibletopical composition.

When sweetening agents (sweeteners) are used, those sweeteners wellknown in the art, including both natural and artificial sweeteners, maybe employed. The sweetening agent used may be selected from a wide rangeof materials including water-soluble sweetening agents, water-solubleartificial sweetening agents, water-soluble sweetening agents derivedfrom naturally occurring water-soluble sweetening agents, dipeptidebased sweetening agents, and protein based sweetening agents, includingmixtures thereof. Without being limited to particular sweetening agents,representative categories and examples include:

(a) water-soluble sweetening agents such as monosaccharides,disaccharides and polysaccharides such as xylose, ribose, glucose(dextrose), mannose, galactose, fructose (levulose), sucrose (sugar),maltose, invert sugar (a mixture of fructose and glucose derived fromsucrose), partially hydrolyzed starch, corn syrup solids,dihydrochalcones, monellin, steviosides, and glycyrrhizin, and mixturesthereof;

(b) water-soluble artificial sweeteners such as soluble saccharin salts,i.e., sodium or calcium saccharin salts, cyclamate salts, the sodium,ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(Acesulfame-K), the free acid form of saccharin, and the like;

(c) dipeptide based sweeteners, such as L-aspartic acid derivedsweeteners, such as L-aspartyl-L-phenylalanine methyl ester (Aspartame)and materials described in U.S. Pat. No. 3,492,131,L-alpha-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alanin-amidehydrate (Alitame), methyl esters of L-aspartyl-L-phenylglycerine andL-aspartyl-L-2,5-dihydrophenyl-glycine,L-aspartyl-2,5-dihydro-L-phenylalanine;L-aspartyl-L-(1-cyclohexen)-alanine, and the like;

(d) water-soluble sweeteners derived from naturally occurringwater-soluble sweeteners, such as chlorinated derivatives of ordinarysugar (sucrose), e.g., chlorodeoxysugar derivatives such as derivativesof chlorodeoxysucrose or chlorodeoxygalactosucrose, known, for example,under the product designation of Sucralose; examples ofchlorodeoxysucrose and chlorodeoxygalacto-sucrose derivatives includebut are not limited to: 1-chloro-1′-deoxysucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-alpha-D-fructofuranoside, or4-chloro-4-deoxygalactosucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-1-chloro-1-deoxy-beta-D-fructo-furanoside,or 4,1′-dichloro-4,1′-dideoxygalactosucrose;1′,6′-dichloro-1′,6′dideoxysucrose;4-chloro-4-deoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructo-furanoside,or 4,1′,6′-trichloro-4,1′,6′-trideoxygalacto-sucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-6-chloro-6-deoxy-beta-D-fructofuranoside,or 4,6,6′-trichloro-4,6,6′-trideoxygalactosucrose;6,1′,6′-trichloro-6,1′,6′-trideoxysucrose;4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-di-deoxy-beta-D-fructofuranoside,or 4,6,1′,6′-tetrachloro-4,6,1′,6′-tetradeoxygalacto-sucrose; and4,6,1′,6′-tetrachloro-4,6,1′,6′-tetradeoxy-sucrose; and

(e) protein based sweeteners such as thaumaoccous danielli (Thaumatin Iand II).

In general, an effective amount of sweetening agent is utilized toprovide the level of sweetness desired in the particular ingestibletopical composition, and this amount will vary with the sweetenerselected and the final ingestible product desired. The amount ofsweetener normally present is in the range from about 0.0025% to about90%, by weight of the ingestible topical composition, depending upon thesweetener used. The exact range of amounts for each type of sweetener iswell known in the art and is not the subject of the present invention.

The flavoring agents (flavors, flavorants) which may be used includethose flavors known to the skilled artisan, such as natural andartificial flavors. Suitable flavoring agents include mints, such aspeppermint, citrus flavors such as orange and lemon, artificial vanilla,cinnamon, various fruit flavors, both individual and mixed, and thelike.

The amount of flavoring agent employed in the ingestible topicalcomposition is normally a matter of preference subject to such factorsas the type of final ingestible composition, the individual flavoremployed, and the strength of flavor desired. Thus, the amount offlavoring may be varied in order to obtain the result desired in thefinal product and such variations are within the capabilities of thoseskilled in the art without the need for undue experimentation. Theflavoring agents, when used, are generally utilized in amounts that may,for example, range in amounts from about 0.05% to about 6%, by weight ofthe ingestible topical composition.

Suitable buffer solutions useful in the non-ingestible topical flavoringagents include citric acid-sodium citrate solution, phosphoricacid-sodium phosphate solution, and acetic acid-sodium acetate solutionin amounts up to about 1%, and preferably from about 0.05% to about 0.5%by weight of the ingestible topical composition.

In accordance with this invention, organoleptically effective amounts ofthe flavoring agents of the present invention may be admixed with aningestible topical vehicle to form a topical composition. These amountsare readily determined by those skilled in the art without the need forundue experimentation. In a preferred embodiment, the ingestible topicalflavoring agents will comprise the flavoring agent in an amount fromabout 0.025% to about 2% and an ingestible topical vehicle in a quantitysufficient to bring the total amount of composition to 100%, by weightof the ingestible topical composition. In a more preferred embodiment,the ingestible topical flavoring agents will comprise the flavoringagent in an amount from about 0.05% to about 1% and an ingestibletopical vehicle in a quantity sufficient to bring the total amount ofcomposition to 100%, by weight of the ingestible topical composition.

The present invention extends to methods for preparing the ingestibletopical flavoring agents. In such a method, the ingestible topicalcomposition is prepared by admixing an organoleptically effective amountof the flavoring agent of the present invention and an ingestibletopical vehicle. The final compositions are readily prepared usingstandard methods and apparatus generally known by those skilled in thepharmaceutical arts. The apparatus useful in accordance with the presentinvention comprises mixing apparatus well known in the pharmaceuticalarts, and therefore the selection of the specific apparatus will beapparent to the artisan.

In a preferred embodiment, an ingestible topical composition is made byfirst dissolving coloring agents, sweetening agents, and similaradditives in water. The flavoring agent is then admixed with the aqueoussolution. Then sufficient water or ethanol, or mixtures of water andethanol, are added to the solution with mixing until the final solutionvolume is reached. In a more preferred embodiment, the flavoring agentis added to the solution as the final ingredient. The final ingestibletopical flavoring agents are readily prepared using methods generallyknown in the pharmaceutical arts.

The ingestible composition may also be in the form of dental gel. Asused herein, the term “gel” means a solid or semisolid colloid whichcontains considerable quantities of water. The colloid particles in agel are linked together in a coherent meshwork which immobilizes thewater contained inside the meshwork.

The dental gel compositions of the present invention may contain theconventional additives set out above for ingestible topical flavoringagents such as mouthwashes, rinses, ingestible sprays, and suspensionsand, in addition, may contain additional additives such as a polishingagent, a desensitizing agent, and the like, providing the additionaladditives do not interfere with the properties of the composition.

In a dental gel composition, the ingestible vehicle generally compriseswater, typically in an amount from about 10% to about 90%, by weight ofthe dental gel composition. Polyethylene glycol, propylene glycol,glycerin, and mixtures thereof may also be present in the vehicle ashumectants or binders in amounts from about 18% to about 30%, by weightof the dental gel composition. Particularly preferred ingestiblevehicles comprise mixtures of water with polyethylene glycol or waterwith glycerin and polypropylene glycol.

The dental gels of the present invention include a gelling agent(thickening agent) such as a natural or synthetic gum or gelatin.Gelling agents such as hydroxyethyl cellulose, methyl cellulose,glycerin, carboxypolymethylene, and gelatin and the like, and mixturesthereof may be used. The preferred gelling agent is hydroxyethylcellulose. Gelling agents may be used in amounts from about 0.5% toabout 5%, and preferably from about 0.5% to about 2%, by weight of thedental gel composition.

The dental gel compositions of the present invention may also include apolishing agent. In clear gels, a polishing agent of colloidal silicaand/or alkali metal aluminosilicate complexes is preferred since thesematerials have refractive indices close to the refractive indices of thegelling systems commonly used in dental gels. In non-clear gels, apolishing agent of calcium carbonate or calcium dihydrate may be used.These polishing agents may be used in amounts up to about 75%, andpreferably in amounts up to about 50%, by weight of the dental gelcomposition.

The dental gel may also contain a desensitizing agent such as acombination of citric acid and sodium citrate. Citric acid may be usedin an amount from about 0.1% to about 3%, and preferably from about 0.2%to about 1%, by weight, and sodium citrate may be used in an amount fromabout 0.3% to about 9%, and preferably from about 0.6% to about 3%, byweight of the dental gel composition.

In accordance with this invention, organoleptically effective amounts ofthe flavoring agents of the present invention may be admixed into thedental gel compositions. These amounts are readily determined by thoseskilled in the art without the need for undue experimentation. In apreferred embodiment, the dental gel compositions will comprise theflavoring agent in an amount from about 0.025% to about 2% and aningestible topical vehicle in a quantity sufficient to bring the totalamount of composition to 100%, by weight of the dental gel composition.In a more preferred embodiment, the dental gel compositions willcomprise the flavoring agent in an amount from about 0.05% to about 1%and an ingestible topical vehicle in a quantity sufficient to bring thetotal amount of composition to 100%, by weight of the dental gelcomposition.

The present invention extends to methods for preparing the stabilizeddental gel compositions. In such a method, the dental gel composition isprepared by admixing an organoleptically effective amount of theflavoring agent of the present invention and an ingestible topicalvehicle. The final compositions are readily prepared using methodsgenerally known by those skilled in the dental and pharmaceutical arts.The apparatus useful in accordance with the present invention comprisesmixing apparatus well known in the pharmaceutical arts, and thereforethe selection of the specific apparatus will be apparent to the artisan.

In a preferred embodiment, an dental gel composition is made by firstdispersing a gelling agent in a humectant or water, or a mixture ofboth, then admixing to the dispersion an aqueous solution of thewater-soluble additives such as the fluorine providing compound,sweeteners and the like, then adding the polishing agent, and lastlyadmixing the flavoring agent and the flavoring agent. The final gelmixture is then tubed or otherwise packaged. The liquids and solids in agel product are proportioned to form a creamy or gelled mass which isextrudable from a pressurized container or from a collapsible tube. Thefinal flavoring agents are readily prepared using methods generallyknown in the pharmaceutical arts.

Throughout this application, various publications have been referenced.The disclosures in these publications are incorporated herein byreference in order to more fully describe the state of the art.

The present invention is further illustrated by the following exampleswhich are not intended to limit the effective scope of the claims. Allparts and percentages in the examples and throughout the specificationand claims are by weight of the final composition unless otherwisespecified.

EXAMPLE 1

This example illustrates the preparation of ethyl 3-mercaptobutyraterepresented by the formula, CH₃(SH)CHCH₂COOCH₂CH₃, in purified form,unaccompanied by substances of natural origin present in mango.

Ethyl 3-mercaptobutyrate was prepared by reacting ethyl crotonate withsodium hydrogen sulfide and sodium bicarbonate in water, at roomtemperature, to form the disulfide dimer of the product.

Disulfide Dimer of Ethyl 3-Mercaptobutyrate

The disulfide dimer of ethyl 3-mercaptobutyrate was then reduced withzinc in acetic acid to yield the desired product, ethyl3-mercaptobutyrate.

The reaction mixture was then concentrated under vacuum, diluted withwater, extracted with ether, dried over sodium sulfate, andconcentrated. Distillation of the crude material at 76–80° C. and 10mmHg gave ethyl 3-mercaptobutyrate in 50% yield and 97% purity. Thestructure was confirmed by mass spectroscopy, nuclear magnetic resonancespectroscopy, and infra red spectroscopy (not shown).

EXAMPLE 2 Flavor Ingredient Evaluation Results

This example summarizes the flavor evaluation results obtained todetermine whether the novel flavoring agent of the present invention,ethyl-3-mercaptobutyrate, has a significant and desirable effect on theflavor profile when added to mango and pineapple flavors.

Procedure

A control base flavor was prepared for each flavor type, mango andpineapple. To each base, the test material, ethyl-3-mercaptobutyrate,was added at concentration levels of 0.0001%, 0.001% and 0.01%. Tastingsolutions were prepared containing sugar at 7%. The mango flavors weredosed at 0.035% and the pineapple flavors were dosed at 0.05%. Sixflavorists participated in a blind tasting. The flavorists were asked totaste and describe the control base, to taste the other samples, tocompare the odor and flavor characteristics with that of the base, andto indicate their preferred sample.

Results

a) Mango

Sample Concentration* Preference Flavor and Odor Descriptors Base    0%0 Juicy, skin, tropical, fruity, herbal, creamy 1 0.0001% 3 Increase intropical, ripe and fruity notes 2  0.001% 2 More impact than base, ripe,over-ripe, sulfury, more tropical 3  0.01% 1 Over-ripe, rotten,tropical, pineapple, skunk, sulfury *Concentration ofethyl-3-mercaptobutyrate.

These results show that ethyl 3-mercaptobutyrate alters the flavorcomposition and at the levels of 0.0001%–0.001% imparts tropical, ripe,and fruity notes with more impact than the mango base. The mostpreferred flavoring sample was Sample (1) which contained 0.001% ofethyl 3-mercaptobutyrate. This was determined to be more characteristicthan the other samples.

b) Pineapple

Sample Concentration* Preference Flavor and Odor Descriptors Base    0%0 Juicy, fruity, fleshy, tropical, creamy, ripe 4 0.0001% 1 Increase intropical, ripe and fruity notes 5  0.001% 4 More impact than base, ripe,sulfury, canned more tropical and fruity 6  0.01 % 1 Over-ripe, rotten,unbalanced, sulfury and skunky *Concentration ofethyl-3-mercaptobutyrate.

These results show that ethyl 3-mercaptobutyrate alters the flavorcomposition and at the level of 0.001% imparts more impact than thepineapple base with ripe, sulfury, canned, tropical, and fruity notes.The most preferred flavoring sample was Sample (5) which contained0.0001% of ethyl 3-mercaptobutyrate. This was determined to be morecharacteristic than the other samples.

In summary, the panel results show that the odor and tastecharacteristics of the ethyl 3-mercaptobutyrate flavor chemical of thepresent invention has a beneficial effect on the overall profile ofmango and pineapple flavors. The average hedonic score for ethyl3-mercaptobutyrate on a scale of 1–9 where 9 is most preferred was 7.1.The average score for many currently used flavor raw materials is about6.0.

EXAMPLE 3 Fragrance Ingredient Evaluation Results

This example summarizes the fragrance evaluation results obtainedcomparing the novel fragrance agent of the present invention versuscontrol compounds.

Mango Fragrance

A base mango control fragrance composition was prepared and used as acontrol at the following levels.

Ingredient Name Formula Parts LINALOL PURE 47.5560 HEDIONE 12.6816DIPROPYLENE GLYCOL LO DPG 7.5829 CITRONELLOL 950 5.5482 ALPHA TERPINEOLUC. 4.7556 GAMMA OCTALACTONE 3.1704 BETA PINENE LO 2.3778 CIS 3 HEXENOL2.3778 GAMMA DECALACTONE 2.3778 ETHYL ACETATE FOOD SOLV QUAL 1.9022CIS-3-HEXENYL ACETATE 1.5852 ETHYL 2 METHYL BUTYRATE 1.2682 ETHYLBUTYRATE 1.2682 CIS JASMONE 0.9511 ISO-AMYL ACETATE 0.9511 ETHYLCAPROATE 0.7926 ALLYL ISO-AMYLOXYACETATE 0.7926 DAMASCENONE 0.6341 LAEVOROSE OXIDE 0.4756 METHYL NONYLENATE 0.4756 VANILLIN FCC POWDER 0.3170GALBANOLENE SUPER 0.1585 Totals 100.000

Ethyl 3-mercaptobutyrate was then added to the base mango controlfragrance composition at the following level, 0.1% to replace the 7.58%of dipropylene glycol. In summary, the panel results show that the mangoodor and characteristics of the ethyl 3-mercaptobutyrate fragrancechemical of the present invention was preferred in every case over thecontrol and hence has a beneficial effect on the overall profile oftropical fruit fragrance.

The invention being thus described, it will, be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention and all suchmodifications are intended to be included within the scope of thefollowing claims.

1. A method for flavoring an ingestible composition which comprisesadmixing an ingestible vehicle with an organoleptically effective amountof ethyl 3-mercaptobutyrate represented by the formula,CH₃(SH)CHCH₂COOCH₂CH₃ in purified form, unaccompanied by substances ofnatural origin present in mango.
 2. The method according to claim 1,wherein ethyl 3-mercaptobutyrate is present in the ingestiblecomposition in an amount from about 0.001% to about 1%, by weight. 3.The method according to claim 2, wherein ethyl 3-mercaptobutyrate ispresent in the ingestible composition in an amount from about 0.1% toabout 0.50%, by weight.
 4. The method according to claim 1, wherein theingestible, composition is a beverage product.
 5. The method accordingto claim 1, wherein the ingestible composition is a confectionerycomposition.
 6. The method according to claim 1, wherein the ingestiblecomposition is a chewing gum.